Bi(OTf)3 catalyzed synthesis of acyclic β-sulfanyl ketones via a tandem Meyer-Schuster rearrangement/conjugate addition reaction

Article abstract of DOI:10.1016/j.tetlet.2019.06.064

A new strategy to prepare acyclic β-carbonyl thioethers from propargyl alcohols and sulfur nucleophiles is reported. The investigation of the reaction substrates scope indicated that primary 3-aryl propargyl alcohols and thiols underwent the transformation smoothly. The reaction probably proceeded a Bi(OTf)₃-catalyzed tandem Meyer-Schuster rearrangement of 3-aryl propargyl alcohol, followed by a thiol Michael conjugate addition of thiols to in situ generated α, β-unsaturated ketones. The method was 100% atom economic, high-yielding, and easy to handle, making it a valuable method for the construction of β-carbonyl sulfides.

Full text of DOI:10.1016/j.tetlet.2019.06.064

Accepted Manuscript
Bi(OTf)3 catalyzed synthesis of acyclic β-sulfanyl ketones via a tandem Meyer-
Schuster rearrangement/conjugate addition reaction
Yuan Wang, Yan Yin, Qinglin Zhang, Wanyong Pan, Huifeng Guo, Keke Pei
PII:
S0040-4039(19)30635-5
https://doi.org/10.1016/j.tetlet.2019.06.064
TETL 50905
DOI:
Reference:
Tetrahedron Letters
To appear in:
Received Date:
Revised Date:
Accepted Date:
27 May 2019
21 June 2019
27 June 2019
Please cite this article as: Wang, Y., Yin, Y., Zhang, Q., Pan, W., Guo, H., Pei, K., Bi(OTf)3 catalyzed synthesis of
acyclic β-sulfanyl ketones via a tandem Meyer-Schuster rearrangement/conjugate addition reaction, Tetrahedron
Letters (2019), doi: https://doi.org/10.1016/j.tetlet.2019.06.064
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers
we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and
review of the resulting proof before it is published in its final form. Please note that during the production process
errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

Graphical Abstract
To create your abstract, type over the instructions in the template box below.
Fonts or abstract dimensions should not be changed or altered.
Bi(OTf)3 catalyzed synthesis of acyclic
Leave this area blank for abstract info.
β-sulfanyl ketones via a tandem
Meyer-Schuster rearrangement
/ conjugate addition reaction
Yuan Wang a, Yan Yin a,*, Qinglin Zhang a, Wanyong Pana, Huifeng Guo a, Keke Peia
aSchool of Chemical and Environmental Engineering, Shanghai Institute of Technology, 100 Hai Quan Rd.,
Shanghai, 201418, P. R. China.
R1
OH
O
R1
R2
R2
SR3
Bi(OTf)3
R3SH
+
Ar
Dioxane
reflux
Ar
up to 95% yields

1
Tetrahedron Letters
journal homepage: www.elsevier.com
Bi(OTf)3 catalyzed synthesis of acyclic β-sulfanyl ketones via a tandem Meyer-
Schuster rearrangement/conjugate addition reaction
Yuan Wanga, Yan Yina, , Qinglin Zhanga, Wanyong Pana, Huifeng Guoa, Keke Peia
aSchool of Chemical and Environmental Engineering, Shanghai Institute of Technology, 100 Hai Quan Rd., Shanghai, 201418, P. R. China
———
ARTICLE INFO
ABSTRACT
 Corresponding author. Tel.: +1-021-608-7220; fax: +1-021-608-7230; e-mail: yinyan@sit.edu.cn
Article history:
Received
A new strategy to prepare acyclic β-carbonyl thioethers from propargyl alcohols and sulfur
nucleophiles is reported. The investigation of the reaction substrates scope indicated that
Received in revised form
Accepted
Available online
primary 3-aryl propargyl alcohols and thiols underwent the transformation smoothly. The
reaction probably proceeded a Bi(OTf)3-catalyzed tandem Meyer-Schuster rearrangement of 3-
aryl propargyl alcohol, followed by a thiol Michael conjugate addition of thiols to in situ
generated α, β-unsaturated ketones. The method was 100% atom economic, high-yielding, and
easy to handle, making it a valuable method for the construction of β-carbonyl sulfides.
Keywords:
β-carbonyl thioether
Propargyl alcohols
Meyer-Schuster rearrangement
Thiol Michael conjugate addition
Bi(OTf)3
2009 Elsevier Ltd. All rights reserved.
1. Introduction
starting materials readily available method for the synthesis of
acyclic β-carbonyl thioethers.
Acyclic β-carbonyl thioether is an useful building block in
organic synthesis,1 and widely exists in natural products,2 drugs,3
beverages,4 and foods.4 Usually, this moiety is obtained through
thiol Michael addition of α, β-unsaturated ketones and sulfur-
containing nucleophiles.5 Nucleophilic substitution of mercaptan
to β-carbonyl halides under basic conditions afforded an
alternative route to prepare β-carbonyl thioether.6 Gill reported
the synthesis of sulfides through β-acylethylation with ketonic
Mannich bases.7 Wen's group developed a novel acid-promoted
direct cross-coupling reaction of methyl ketones and DMSO to
prepare β-acyl allylic methyl sulfides in 2011.8 Hou et al.
reported an amine-catalyzed one-pot synthesis of thioethers
directly from carboxylic acids, thioureas, and Michael acceptors
in 2015.9 Although methods to construct β-carbonyl thioether are
available, the development of new synthetic methods for this
particular structure remains an important and challenging task for
organic chemists.
Previously work
O
O
OH
Fe(OTf)3
R2
+ R1SO2NHR2
Ar
N
Scheme A
Scheme B
Ar
dixoane/reflux
SO2R1
Present work
R3
OH
R3
R4
R4
SR5
Lewis acid
+
R5SH
Ar
Ar
Figure 1. Conversion of 3-aryl propargyl alcohols
2. Results and discussion
A series of 3-aryl substituted propargyl alcohols (1a-1m, 1n,
and 1p) were prepared through a Pd2+-catalyzed Sonogashira
coupling reaction of Ar-X and commercial available prop-2-yn-
1-ols (Figure 2, Scheme A).11 1,3-Diphenyl-prop-2-yn-1-ols (1o,
1q, and 1r) were formed from the nucleophilic attack of
phenylacetylene towards phenyl carbonyl compounds (Figure 2,
Scheme B).12
Previously, our group reported the synthesis of acyclic β-
aminoketones from 3-aryl propargyl alcohols and nitrogen
nucleophiles, which probable proceeded a Fe(OTf)3 catalyzed
Meyer-Schuster rearrangement of 3-aryl propargyl alcohols,
followed by an intermolecular hydroamination between nitrogen
nucleophiles and α,β-unsaturated ketones. This research also
showed that only primary 3-aryl propargyl alcohols and
sulfonamides underwent the transformation smoothly (Figure 1,
Scheme A).10 As we all know sulfur is highly nucleophilic, we
guessed the replacement of sulfonamides with sulfur alcohols
would allow the formation of acyclic β-carbonyl thioethers from
3-aryl propargyl alcohols (Figure 1, Scheme B). Herein, the
scopes of propargyl alcohols and sulfur nucleophiles were
investigated, which provided an 100% atom economic and
R
2 OH
OH
Scheme A
PdCl2(PPh3)2, CuI
Et3N, 80oC
R1
+
R1
R2
Ar-X
+
Ar
1a-1m 1n
1p
,
, and
R
3 OH
O
n-BuLi
Scheme B
Ph
R3
THF, -78oC, rt.
Ph
1o, 1q,
1r
and
Figure 2. Synthesis of 1.
To efficiently prepare acyclic β-carbonyl sulfides, we screened
reaction conditions using 3-phenylprop-2-yn-1-ol (1a) and
phenylmethanethiol (2a) as the starting materials (Table 1).
When 15 mol% TfOH, Fe(OTf)3, FeCl3, and Cu(OTf)2 were used
as the catalyst, 54%–78% moderate yields of 3-(benzylthio)-1-
phenylpropan-1-one (3a) were achieved after refluxing in

2
Tetrahedron
c The unconsumed 1a was recovered.
dioxane for 8 h (Entries 1-4). The complete disappearance of
1a was detected by TLC after 30 h using 15 mol% AgOTf as the
catalyst, and a 62% yield was obtained (Entry 5). When 15 mol%
Bi(OTf)3 was added, the yield of 3a reached 93% in 2 h with
dioxane as the solvent (Entry 6). Reaction solvents were tested
with 15 mol% Bi(OTf)3 as the catalyst, the reaction mixtures
were quite complex probably due to the side reactions between
2a and the solvents when (trifluoromethyl)benzene and DCE
were used as the solvents,13 and 45% and 38% yields were
observed, respectively (Entries 7 and 8). Reaction with toluene
gave only a 15% yield, and the unconsumed 1a was recovered
(Entry 9). The investigation of catalyst loading indicated that
increasing the amount of Bi(OTf)3 from 15 mol% to 20 mol%
caused no effect on the yields compared entry 10 with 6, but
decreasing the catalyst loading to 10 mol% lowed the reaction
rate and yield (Entry 11 vs. 6). A 1a:2a ratio of 1 gave lower
yields over longer reaction times because a small amount of 2a
was oxidized to 1,2-dibenzyldisulfane (Entry 12 vs. 6).
Increasing the 1a:2a ratio to 1.2 produced same 93% yield to
1a:2a ratio of 1.1 (Entry 13 vs. 6). No reaction occurred between
1a and 2a without catalyst (Entry 14). 2-Methylene-1,5-
diphenylpentane-1,5-dione was separated after refluxing the
mixture of 1a in dioxane for 5 h (Entry 15).14 The optimized
reaction conditions for further studies were 15 mol% Bi(OTf)3 as
the catalyst, the 1.1 ratio of propargyl alcohol and sulfur
nucleophiles as starting materials, and dioxane as the solvent.
Previously, we found the reaction with amide and aniline as
the nitrogen nucleophiles could not give the corresponding
acyclic β-aminoketones because of low nucleophilicity,10 so we
investigated the scope of commercially available sulfur-
containing nucleophiles. The transformations of thiols, including
phenylmethanethiols, benzenethiols, and aliphatic thiols, to β-
carbonyl thioethers were fast and high-yield (Table 2). However,
replacing thiols with urea did not produce the desired products
after 16 h (data not shown here). 2b with F and 2c with Cl at 4
position of the benzyl ring produced similar yields to 2a after
refluxing 5 h (90% yield for 2b and 95% yield for 2c vs 93% for
2a. Entries 2 and 3 vs Entry 1). Benzenethiols with F, Cl, CH3,
and OCH3 at the para-position of the phenyl ring gave the
corresponding β-carbonyl thioethers in good yield after 5 h
(Entries 4-7), but the yields of substrates with electron-donating
groups were lower than with electron-withdrawing groups
because more thiols 2 were converted to disulfides. Aliphatic
thiols 2h and 2i were submitted the investigation, both of them
gave the expected products in 92% yields (Entries 8 and 9).
a
Table 2. Scope of the sulfur-containing nucleophiles
O
Bi(OTf)3
OH
RSH
Ph
SR
Ph
dioxane/reflux
1a
2
3
Table 1. Optimization of the reaction conditionsa
Yield
(%)b
Entry
Thiol
Product
Time(h)
2
O
O
OH
Cat.
SH
Ph
SH
Ph
S
Ph
S
Ph
1
2
93
90
reflux
2a
2b
2c
3a
3a
1a
2a
O
SH
Catalyst
loading
(mol%)
Ratio
of
2a:1a
Time
(h)
Yield
of 3a
(%)b
S
5
5
F
Entry
Catalyst
Solvent
F
3b
O
SH
1
2
3
4
5
6
7
TfOH
Fe(OTf)3
FeCl3
Dioxane
Dioxane
Dioxane
Dioxane
Dioxane
Dioxane
15
15
15
15
15
15
15
1.1
1.1
1.1
1.1
1.1
1.1
1.1
8
8
54
60
62
78
62
93
45
S
Cl
3
4
5
95
89
90
Cl
F
3c
O
SH
8
S
5
5
F
3d
2d
Cu(OTf)2
AgOTf
8
Cl
O
30
2
SH
S
Cl
3e
Bi(OTf)3
Bi(OTf)3
2e
SH
O
(Trifluor
omethyl)
benzene
DCE
2
S
6
7
5
5
83
70
2f
3f
OCH3
SH
8
Bi(OTf)3
Bi(OTf)3
Bi(OTf)3
Bi(OTf)3
Bi(OTf)3
Bi(OTf)3
15
15
20
10
15
15
1.1
1.1
1.1
1.1
1
2
2
2
5
3
2
38
15c
93
86
85
93
O
S
H3CO
2g
9
Toluene
Dioxane
Dioxane
Dioxane
Dioxane
3g
O
10
11
12
13
SH
S
8
9
5
3
92
92
2h
3h
O
S
SH
2i
3i
1.2
aReaction conditions: 1a (0.2 mmol), RSH (0.22 mmol), Bi(OTf)3 (0.03
mmol), dioxane (1 mL), 110 O
C
14
15
-
Dioxane
Dioxane
-
1.1
-
2
5
NRc
NR
bIsolated yield after flash chromatography.
Bi(OTf)3
15
Yanada reported that only 3-phenylprop-2-yn-1-ol derivatives
with electronic donating grousp on the phenyl ring underwent
Bi(OTf)3-catalyzed tandem Meyer-Schuster rearrangement and
a Reaction conditions: 1a (0.2 mmol), solvent (1mL), reflux.
b Isolated yield after flash chromatography.

3
O
intramolecular 1,4-addition to the resulting vinyl ketone.14 We
then explored the scope of propargyl alcohols with 2a as the
sulfur nucleophile (Table 3). Propargyl alcohols (1a-1m) with
different electron densities on the carbon-carbon triple bond were
prepared according to Scheme A in Figure 2 by changing the
aryl groups α to the triple bond. The substituents at the 4-position
of the phenyl ring had obvious effects on the reaction times and
yields (Entries 1-11). 1b with fluorine, 1c with chlorine, and 1d
with bromine finished the conversation in good yields after
refluxing longer times compared with 1a (83% for 1b in 5 h,
69% for 1c in 20 h, and 78% for 1d in 16 h, entries 2-4). It is
worth noting that the reaction of 1b proceeded faster than 1c and
1d probably because of the complex interactions existing in 1b.15
However, there were no transformation for substrates with very
electron-withdrawing groups (1e with NO2 and 1f with CN), and
the starting materials were recovered (Entries 5 and 6). 1g with
methyl group showed similar reactivity to 1a (Entry 7). Methoxy
groups at para or ortho positions of the phenyl ring were
favorable for the reaction rate because of the higher electron
density of carbon-carbon triple bond, and 4h and 4i were
achieved in high yield after 0.5 h (Entries 8 and 9). Changing the
aromatic group at the carbon-carbon triple bond from phenyl
group to biphenyl, naphthyl, and thienyl groups did no cause
pronounced effects on the reaction, and 4k-4m were separated in
excellent yields (Entries 11-13). However, the expected products
were not detected when the Ar groups in 1 were replaced by
methyl group or ethyl group.
OH
SBn
12
13
2
2
90
95
4l
1l
O
OH
SBn
S
1m
S
4m
aReaction conditions: 1a (0.2 mmol), RSH (0.22 mmol), Bi(OTf)3 (0.03
mmol), dioxane (1 mL)，110 OC.
bIsolated yield after flash chromatography.
cThe unconsumed 1a was recovered.
After investigating primary propargyl alcohols, we turned our
attention to secondary and tertiary propargyl alcohols. The results
showed that all propargyl alcohols with bulky group α to -OH
(1n-1r) completely disappeared within 1.5 h under the optimized
condition (Table 4). The alcohols 1n-1q produced β-carbonyl
thioethers in 30%-45% yields, and unexpected by-products, such
as benzyl(3-phenylprop-2-yn-1-yl)sulfanes and α,β-unsaturated
ketones, were separated (Entries 1-4). When 1r, with two Ph
groups α to -OH, gave only 1,3,3-triphenylprop-2-en-1-one in
90% yield via Meyer-Schuster rearrangement (Entry 5).
Table 4. Scope of 3-phenyl propargyl alcohols 1.a
O
R1
HO
Bi(OTf)3
R2
R2
2a
+
Ph
SBn
Ph
dioxane,reflux
R1
1
4
Time
(h)
Yield of
Table 3. Scope of propargyl alcohols 1.a
Entry
Alcohol
By product
complex
4 (%)b
O
OH
Bi(OTf)3
OH
2a
R
1
2
Ph
1.5
1
45
40
dioxane/reflux
R
SBn
1n
1
4
Ph
S
OH
Ph
Ph
Ph
Ph
Entry
1
Alcohol
Product
O
Time(h)
2
Yield (%)b
93
Ph
1o
A
OH
45% yield
SBn
1a
3a
OH
O
OH
3
4
5
1
1
1
40
30
-
complex
F
SBn
1p
2
3
5
83
69
1b
F
4b
O
O
Ph
OH
Cl
Br
SBn
SBn
Ph
Ph
Ph
Ph
OH
1c
20
B
Cl
4c
1q
1r
40% yield
Ph
O
O
Ph
OH
Ph
OH
OH
Ph
Ph
90% yield
4
1d
16
78
C
Br
4d
aReaction conditions: 1a (0.2 mmol), RSH (0.22 mmol), Bi(OTf)3 (0.03
O
2N
mmol), dioxane (1 mL), 110 OC.
5
6
1e
1f
-
72
72
NRc
NRc
bIsolated yield after flash chromatography.
OH
NC
Combining the knowledge of the transformation of propargyl
-
alcohols into α,β-unsaturated ketones (Table 4),14,16 and the
OH
H3C
O
separation of dimeric diketone, we proposed
a possible
SBn
7
8
9
2
85
85
92
1g
mechanism for the present Bi(OTf)3-catalyzed transformation of
propargylic alcohols (Figure 3). Propargylic alcohols easily
formed intermediate α,β-unsaturated ketones in the presence of
catalytic amounts of Bi(OTf)3, which underwent a nucleophilic
attacked by thiols to afford β-carbonyl thioethes. In alterative,
self-coupling of intermediate α,β-unsaturated ketones led to
dimeric diketone.
H
3C
4g
O
OH
SBn
H3CO
0.5
0.5
1h
H3CO
4h
O
OH
SBn
OCH3
OCH3
1i
4i
O
H3CO
O
OH
SBn
R1SH
O
R1S
Ar
10
11
3
2
86
90
Bi(OTf)3
1j
Ar
OCH3
Ar
O
O
4j
OH
O
OH
Ar
Ar
Ph
SBn
unsaturated ketone
1k
Ph
4k
Figure 3. Proposed mechanism

4
Tetrahedron
12. Song, X. R.; Han, Y. P.; Qiu, Y. F.; Qiu, Z. H.; Liu, X. Y.; Xu, P.
F.; Liang Y. M. Chem. Eur. J. 2014, 20, 12046–12050.
3. Conclusion
13. (a) Chernov, G. N.; Levin, V. V.; Kokorekin, V. A.; Struchkova,
M. I.; Dilman, A. D. Adv. Synth. Catal. 2017, 359; (b)Raasch, M.
S. J. Org. Chem.1980, 45,856-867.
14. Okamoto, N.; Sueda, T.; Yanada, R. J. Org. Chem. 2014, 79,
9854-9859.
15. Larisa, V. P.; Igor, P. C.; Evgeny, V. T.; Vitalij, D. S.; Ludmila, P.
O.; Olga, D. Z.; Georgy, A. N. J. Fluorine Chem. 2015, 178,142-
153.
16. (a)Bhuvaneswari, S.; Jeganmohan, M.; Cheng, C. H. Chem. Asian.
J., 2010, 5, 141-146; (b) Egi, M.; Yamaguchi, Y.; Fujiwara, N.;
Akai, S. Org. Lett. 2010, 39, 1867-1870.
17. Typical procedure: To a mixture of propargyl alcohol 1 (0.2
mmol) in dioxane (1 mL), Bi(OTf)3 (0.03 mmol) and nucleophile
2 (0.22 mmol) were added. The mixture was stirred at refluxing
temperature until 1 disappeared monitored by TLC. Then the
reaction was quenched by saturated NaHCO3 solution and
extracted with ethyl acetate. The combined organic phases were
washed with brine, dried over anhydrous Na2SO4 and concentrated
under reduced pressure to give a residue. Finally the residue was
purified through column chromatography on silica gel (200-300
mesh) with hexane/EtOAc as eluent to afford the products 3a-3i,
4b-4d, and 4g-4q. 3-(benzylthio)-1-phenylpropan-1-one (3a): 92%
yield; yellow oil; 1H NMR (500 MHz, Chloroform-d) δ 7.92 –
7.86 (m, 2H), 7.56 (t, J = 7.5 Hz, 1H), 7.45 (t, J = 7.5 Hz, 2H),
7.35 – 7.29 (m, 4H), 7.24 (s, 1H), 3.77 (s, 2H), 3.17 (t, J = 7.5 Hz,
2H), 2.84 (t, J = 7.5 Hz, 2H). 13C NMR (125 MHz, Chloroform-d)
δ 198.30 , 138.38 ,136.60 , 133.23 , 128.87 , 128.64 , 128.58 ,
128.03 , 127.08 , 38.75 , 36.92 , 25.88 . IR (KBr, cm-1) 3726,
3647, 3470, 2957, 2918, 1683, 1596, 1560, 1492, 1448, 1378,
1019, 979, 748, 695, 491.
In summary, we developed a Bi(OTf)3-catalyzed preparation
of acyclic β-carbonyl sulfides17 from 3-aryl propargyl alcohols
and thiols, which probably proceeded by tandem Meyer-Schuster
rearrangement of propargyl alcohols, followed by the
nucleophilic attack of thiols on α,β-unsaturated ketones. The
starting material was easy to obtain, the experimental process
was simple. Few by-products, high yields, and 100% atomic
utilization rate make it a potentially attractive method for the
synthesis of acyclic β-carbonyl sulfides. Reactions with
propargyl alcohols as nucleophiles were currently underway in
our lab and will be published in due course.
Acknowledgments
Financial supports from National Natural Science Foundation
of China (Grant No. 21502117), Shanghai Municipal Education
Commission (Plateau Discipline Construction Program ), and the
collaboration Innovation Foundation of Shanghai Institute of
Technology, China (No.XTCX2016-3). We are also grateful to
Prof. Gang Zhao and Prof. Guanjun Wang for technical
assistance.
Supplementary data
Supplementary data associated with this article can be
found in the online version at http://dx.doi.org.
References and notes
1.
(a)Castagnolo, D.; Lauder, K.; Toscani, A.; Qi, Y.; Korah, K.
Angew. Chem. Int. Ed. 2018, 57, 5803-5807; (b)Ulendeeva, A. D.;
Baeva, L. A.; Valiullin, O. R.; Nikitina, T. S.; Arslanova, D. D.;
Spirikhin, L. V. Pet. Chem. 2006, 46, 122-126. (c)Reich, H. J.;
Jasperse, C. P.; Renga, J. M. J. Org. Chem. 1987 , 18. 2981-2988.
(d)Trost, B. M. Chem. Rev. 1978, 78, 363-382.
2.
3.
Reinaldo, R. V.; Etelvino, J. H. B.; Liliana, M.; Blanka, W.
Tetrahedron: Asymmetry. 1999, 10, 3219–3227
(a) Park, H. B.; Kim, Y. J.; Park, J. S.; Yang, H. O.; Lee, K. R.;
Kwon, H. C. Nat. Prod. 2011，74, 2309-2312． (b)Li, L. Y.; Li
D. H.; Luan, Y. P.; Gu, Q. Q.; Zhu, T. J. Nat. Prod. 2012, 75, 920-
927．
4.
(a)Ncrenberg, S.; Kiske, C.; Reichardt, B.; Andelfinger, V.;
Pfeiffer, A.; Schmidts, F. J. Agric. Food Chem. 2017, 65, 8913–
8922. (b) Takoi, K.; Degueil, M.; Shinkaruk, S.; Thibon, C.;
Maeda, K.; Ito, K.; Bennetau, B.; Dubourdieu, D.; Tominaga, T. J.
Agric. Food Chem. 2009, 57, 2493–2502;
5. (a) Lin, Y. M.; Lu, G. P.; Cai, C.; Yi, W. B. RSC Adv. 2015, 5,
27107-27111. (b)Abaee, M. S.; Cheraghi, S.; Navidipoor, S.;
Mojtahedi, M. M.; Forghani, S. Tetrahedron Lett. 2012, 43, 4405-
4408; (c) Kitanosono, T.; Sakai, M.; Ueno, M.; Kobayashi, Shū.
Org. Biomol. Chem. 2012, 10, 7134-7147; (d) Garg ,S. K.; Kumar,
R.; Chakraborti, A. K. Tetrahedron Lett. 2005, 46, 1721-1724; (e)
Habib, F.;Nasser, I.; Abbas, A. J. Synlett. 2005 , 299 -303; (f)
Gorthey, L. N.; Vairamani, M.; Djerassi, C. J. Org. Chem. 1985,
50,4173-4182.
6.
(a) Yadav, J. S.; Reddyb ,V. S.; Baishya, G. Org. Chem., 2003, 68,
7098-7100. (b) Ranu, B. C.;Mandal, T. Synlett. 2007, 6, 925-928
．
7.
8.
9.
Gill, N. S.; James, K. B.; Lions, F.; Potts, K. T. J. Am. Chem. Soc.
1952, 74, 4923-4928.
Wen, Z. K.; Liu, X. H.; Liu, Y. F., Chao, J. B. Org. Lett. 2017, 19,
5798-5801.
Swain, S. P. ; Chou, Y. L.; Hou, D. R. Adv. Synth. Catal. 2015,
357, 2644–2650.
10. Tao, R. H.; Yin, Y.; Duan, Y. B.; Sun, Y. X.; Sun, Y.; Cheng, F.
K.; Pan, J. P.; Lu, C.; Wang, Y. Tetrahedron. 2017, 73, 1762-
1768.
11. Shi, T. D.; Guo, X.; Teng, S. H.; Hu, W. H. Chem. Commun.
2015, 51, 15204–15207.

5
Highlight:
A new strategy to prepare acyclic β-carbonyl
thioethers
Primary 3-aryl propargyl alcohols and thiols
underwent the transformation smoothly
The method was 100% atom economic, high-yielding, and
easy to handle